Microemulsion for oil production

专利摘要:
A micellar slug for use in the recovery of oil, the slug containing a hydrocarbon, an aqueous medium, a surfactant, and a cosurfactant. The surfactant contains as an essential component (a) an internal olefin sulfonate or sulfonates having 10 to 30 carbon atoms and (b) an alpha-olefin sulfonate or sulfonates having 10 to 30 carbon atoms. This micellar slug has a sufficiently low interfacial tension, good salinity tolerance, hard-water resistance, ability to maintain the micro-emulsion against change in the composition of the micro-emulsion, and mobility controlled viscosity.
公开号:SU1349703A3
申请号:SU833623400
申请日:1983-07-18
公开日:1987-10-30
发明作者:Морита Хироси；Кавада Ясуюки；Ямада Юнити；Укигаи Тосиюки
申请人:Лион Корпорейшн (Фирма)；
IPC主号:

专利说明:

The invention relates to a micellar solution injected into a well and used to extract oil from underground oil bearing formations, as well as to the process of extracting or extracting oil residues from underground oil bearing formations.
The aim of the invention is to increase the efficiency of oil recovery by reducing the surface tension between oil and microemulsion.
The proposed micellar solution (MP) for the extraction of oil consists mainly of hydrocarbons, water recycle, surfactant and surfactant. The main components of surfactants are at least one olefin sulfonate with an internal non-limiting bond with 12-24 carbon atoms and at least one sulfonate (A-olefin.
The oil recovery process consists of the following steps: injecting MPs into the wells, injecting at least one liquid nose and bodies together with the MPs and extracting oil from the oil-bearing formations through the wellbore.
The micelle injectable solutions used to extract oil from oil bearing formations are a transparent or translucent liquid microemulsion containing, mash: hydrocarbons 3-60. A mixture of surfactants, the main components of which are olefin sulphonate with 1z-24 carbon atoms and o-olefin sulphonate: with 12-24 carbon atoms, surfactant 0.1-20.
The aqueous medium used as the base MP may be soft water, water containing mineral salts or salt solutions, such as rainwater, water from rivers and lakes, spring water, water contained in the oil reservoir, and also sea water. .
The micelle solutions offered are well resistant to salt solutions and alkali metal salts, so when preparing them you can use water or saline with a concentration of mineral salts up to 25% (preferably up to. 15%). Typical examples of mineral salts in water (or salt solutions) are: NaCl, KCl, KjSOj. For example, in the marine
Water contains about 3.5% of mineral salts containing up to 1600 rrga divalent metal ions, for example, Mg ions (this range of salt concentration is preferred).
The olefin sulfonate used as one of the main components (component a) of surfactants is obtained by sulfonation of olefins containing the mono-olefin with a vinylene radical as an essential component. The number of carbon atoms in olefins is from 10 to 30 (preferably 12-26), the general formula is as follows:
R-CH CH-R,
where R and R are independent hydrocarbon radicals with a straight or branched chain containing 1 or more carbon atoms (preferably 2-12), provided that the total number of carbon atoms in R and R does not exceed 8-28 (preferably 10 -24) Olefins may contain up to 33% (approximately one third) or less of triple-substituted mono-olefins.
The sulfonated products are first neutralized with suitable bases, and then the neutralized product is hydrolyzed.
Thus, the resulting olefin sulfonates contain 20-60% of alkene sulfonates with a double bond and 80-40% of oxyalkane sulfonates, as well as up to 20% of disulfonates. Olefin sulphonates, which differ from those described in structure, can be obtained by selecting the appropriate conditions for sulfonation and hydrolysis. Usually, an increase in the number of carbon atoms in an internal carbon olefin chain leads to an increase in the amount of alkenes sulfonate. An increase in the molar ratio between sulfating agents and olefins in the sulfonation process towards the former leads to an increase in disulfonates.
The olefin sulfonates used to prepare the proposed MP may be alkali metal and alkaline earth metal salts, ammonium salts, as well as organic amino acid salts. Preferred inverse cations are Na, K, Mg, Ca, NH cations, especially Na and Mg.
Examples of the most effective olefin sulfonates used for the proposed MP are olefin sulfonates from 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 12-16, 13-14, 14- 16, 14-18, 15-18, 15-20, 16-18, 16-20, 18-20 and 20-24 carbon atoms, it is possible to combine several olefin sulfonates at once, since this is the most acceptable option from the point of view Accessibility and ease of solution preparation.
The ci-olefins used as the second component (components .c) of surfactants contain 10-30 carbon atoms (preferably 12-26, most preferably 13-24 carbon atoms).
Sulfonates of o-olefins can be alkali and alkaline earth metal salts, ammonium salts, as well as organic salts of amino acids. Preferred inverse cations are Na, K, Mg, Ca, NH cations. Example L. olefin sulfonates can serve dodetsenosulfonat-1, 1-tetradetsenosulfonat, geksadetse- nosulfonat-1, 1-oktadetsenosulfonat, eykozanosulfonat-1, 1-dokotsenosul- methanesulphonate, 1-tetrakotsenosulfonat, d- ol Finns sulfonates with 10-13 carbon atoms, about-olefin sulfonates with 14-16, 14-18, 15-18, 16-18 and 20-24 carbon atoms. These sulphonates can be used both individually and in any mixture;
It is clear that Na salts are cheap and readily available, and alkaline earth metal salts, especially Mg, are resistant to hard water with salts dissolved in it.
The basis of the surfactants included in the micelle solutions is the sulfonates of olefins and oi, α-olefins, the ratio of which is not a constant value, is selected depending on the nature of the oil field and oil-bearing formations used
aqueous medium (or saline) and surfactant and is 19: 1-1: 9 (9: 1-1: 4 ratio is most preferred).
When using only cx, α-olefin sulfonates as surfactants, it is difficult to select the desired composition of the microemulsion for preparing MP, since the range of changes in the composition of these emulsions is small.
When using as a surfactant component, only sulfonates are ole-. Finns with high viscosity, it is difficult to use thickeners that change the viscosity in the right direction, and this, in turn.

leads to an increase in production costs, in addition, thickeners indirectly affect the composition of microemulsions. All these disadvantages can be eliminated using olefin sulfones along with oi-olefins.
The proposed MPs contain 2-30% surfactant, while the preferred concentration is selected taking into account both low tension surfaces and an acceptable cost and is 4-25%. The total amount of olefin sulfonates and oi-olefins, each of which contains 10-30 carbon atoms, must be at least 80% surfactant (preferably 90% or more relative to the total amount of surfactant contained in micellar solutions) .
The hydrocarbons used as an oil component can be distinguished, for example, oil, liquefied petroleum gas (propane-butane fraction), crude gasoline (naphtha), kerosene, diesel fuel and fuel oil. Preference is given to the produced oil due to the low cost and composition corresponding to the composition of the oil remaining in the reservoir. In addition, the sulfonates of olefins and s, α-olefins, which include mainly unreacted olefins or polymerization products, can be considered components of oil.
The proposed MP may contain 3-90% of hydrocarbons. The preferred concentration of hydrocarbons is 5-40% and is optimal for creating a water-oil emulsion.
since large concentrations of hydrocarbons are uneconomical. I
Synthetic surfactants together with surfactants are essential components of microemulsions.
The composition of detergents includes a hydroxyl group of alcohols. The formula for surfactants is as follows:
,,,
where n is a number taking the value
from O to 4,
R is an alkyl or alkylene group containing 3-8 carbon atoms with n O and 1-18 carbon atoms, as well as 7-8 carbon atoms with a phenyl or aralkyl group with n 1 0..
Aliphatic hydrocarbons of the radical R can have either a straight chain or a cent group of branched chains. For example, propanols, butanols, pentanols, hexanols, 2-ethylhexanol or octanols, polyoxylthylenyl hexyl ether (p 1), polioksiztilenovy de tsilovy ether (C 2) j polyoxyethylene tridecyl ether (C 4), butilfenolovy polyoxyethylene ether (n 2) nonnlfenilovy polyoxyethylene ether (n 3), polyoxyethylene dodetsilfenilovy ether (C 4), butoxyethanol and diethylene glycol monobutyl zfira
The proposed MPs can contain 0.1–20% PSA, but a concentration of 1–15% is preferable, which is selected on the basis of the stability of the microemulsion and the decrease in interfacial tension.
The sulfonates of olefins and ci-olefins included in the MP give the solution universality, i.e. allow it to be used for formations and wells of various kinds. Such versatility is due to resistance to hard water and salts, a large range of compositional changes, as well as heat resistance. By changing the ratio of olefin sulfonates and oi-olefins, it is easy to obtain MP with a good ability to retain micro
emulsions and adjustable viscosity.
In addition to the listed components, micelle solutions may also contain additional surfactants, thickeners, or viscosity control agents, if they do not adversely affect the quality of surfactants. for example, such anionic and non-inogenic surfactants such as sulfonates
five
0 5 o
d
five
five
0
five
petroleum, alkyl benzene sulfonates, sulfates of polyoxyethylene acrylate esters, dialkyl sulfosuccinates, sgC — olefin sulfonates, paraffin sulfonates, soaps, higher alcohols of toxoles, alkyl phenol ethoxylates, polyol esters of fatty acids and polyethylene fatty acids, alcohols, alkyl phenol ethoxylates, polyol fatty acid esters and polyethylene fatty acid alcohols, alkyl phenols, ethoxylates
Water-soluble mineral salts, heteropolysaccharides produced by microorganisms, naphthalene sulfate acetalmaldehyde condensates, polyacrylamides, polyacrylates, hydroxyethylcellulose, and carboxymethylcellulose can be used as thickeners.
The proposed MP can be obtained in any existing way. For example, hydrocarbons, surfactants, water-based and synthetic surfactants can be mixed in any sequence using conventional mixers, while maintaining the appropriate temperature and pressure.
MP injection can be performed by any of the known methods for oil production. For example, the MP is injected at 5–90 ° C and a pressure of 1–350 kg / cm to at least one of the production wells, and then under the same conditions a liquid medium is injected therein, which can be water and / or an aqueous solution of one from the listed thickeners, for the transfer or removal of oil from the well. The optimum amount of MP is at least 3%, preferably 5%, but not more than .20% of the porosity of the subterranean formation.
Example 1. The example below shows that microemulsions, that is, MP, can be formed by a combination of olefin sulfonates (IOS) and oi-olefins (AOS) and cannot be used with only ci-olefins.
For evidence of this position, samples were prepared by mixing the surfactant with water. Then, in the process of mixing, surfactants and hydrocarbons were added there.
The composition and properties of the samples are given in table. 1-5.
Interfacial tension was measured with a strain gauge at 25 ° C in an appropriate solution system.
Viscosity was measured at 25 ° C using a Brookfield viscometer.
Example 2 This example demonstrates the possibility of adjusting the viscosity when sharing IOS and AOS as surfactant.
The method of preparation of sample mixtures is the same as in example 1.
The composition and properties of the samples are given in Table. 2-5.
Sample 11, obtained using only IOS, is given for comparison. Sample 15 has a very high viscosity. The remaining samples table. 2 illustrate the invention.
Example 3. This example il-t illustrates the properties of surfactants with different numbers of carbon atoms and metal cations.
Samples were prepared in the same manner as in Example 1. Their properties and. properties are shown in table 3 and 4.
As can be seen from the data table. 1-5, MP is characterized sufficiently:. low interfacial tension, good resistance to salts and hard water, the ability to preserve microemulsions for any changes in their composition and the ability to adjust the viscosity.

权利要求:
Claims (1)
[1]
Invention Formula
Oil displacement microemulsions containing a hydrocarbon, an aqueous electrolyte solution, a surfactant and a co-surfactant, which, in order to increase the efficiency of oil recovery by reducing the surface tension between the oil and the microemulsion, - the microemulsion active substance comprises a mixture of at least one olefinic sulfonate with an internal unsaturated bond with 12-24 carbon atoms and at least one sulfonate of the l-olefin-α. with 12-24 carbon atoms, while the ratio of olefin sulfonates and oi-olefin with an internal unsaturated bond in the mixture is 19: 1-1: 9, the microemulsion contains isopropyl or p-amyl alcohols as a co-surfactant and the components of the microemulsion are taken in the following ratio, wt.%:
Hydrocarbon
Specified surfactant Isopropyl or p-amyl alcohols
Aqueous electrolyte solution
u chG
00Pv)
lO in
And “b
(L and-1
1L ech
in in
mm
see sc
-Sl
cho "
AA
eat g fo
fl4k
about go
- about
ww
 g
Ti MA
--01
) Sz with about
nj
g with
about
about i
3.5
37
,, d 10SNH (CtH + OH) - Cje-Cj IOSNa C "-C, gAOSNaС" -C, in AOSK C, 4-CigAOSNH, Cjo-C AOSNa
4.5
SPAV
Isopropyl alcohol
Amyl alcohol
Hydrocarbon
Kerosene
Mazut Pickle
0.5% NaCl 22% NaCl
 NaCl 8g-ny NaCl Properties
Outlook
- Pull on. surface section
15
70
15
70
40
40 60
Ltd
5 6
25 5
3
thirty
75 60
Ltd
4.5
ten
75
70
1Q 20
65
2.6 38.4 5.8 21.7 57, 3.9 18.4 47.7 3.1
Table $
eleven
5 3,5 - 7 - 7
5 5
7
3
5 6
4.5
40
thirty
1Q 20
25 5
ten
75 60
75
70
65
Ltd
17
nineteen
78 21
48 17
T8 91 93 92 79 83 85
Symbol; o - transparent or translucent homogenized emulsion.
Table 4
Composition
C, 1st ,, lOSNa
C, -C "lOSMg C, 1-C, 4 lOSCa Czo-Ci Na Cjo-Ci Mg C, j-C" AOSMg C, j-C ,,. AOSCa Cjo-C -tAOSNa C o-Cj AOSMg
SPAV
Amyl alcohol
Hydrocarbon Kerosene Fuel Oil
Brine
0.5% NaCl
1349703
18
Continuation of table 3
48 17. 40
13
81 80
5.2
6.5
5.3
4.5 6
4.5
17
5 30
40
20
50
65
- - 50
- 80
75
- - - 68
oh oh oh
on section
cp
55.3 23.4 43.7 0.8 8 12 43 13
Oil recovery efficiency,% 91 89 85 88
Surfactant.
C, -C, 8-olefin sulfonate internal hydrocarbon chain (Na)
C, 4 C 1c sulfonate on α-olefin synthetic detergent (co-agent)
p-Amyl alcohol Hydrocarbon
Liquid fuel Water
1.7 21
89
Table 5
0.1
15
thirty
Oil displacement efficiency,%
Editor L.Beseloveka
Compiled by I. Lopakova
Tehred L. Oliynyk Proofreader M. Demchik
Order 5202/58 Circulation 532 Subscription
VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
Printing and production enterprise, Uzhgorod, st. Project, 4
91
88

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1349703A3|1987-10-30|Microemulsion for oil production

---

US4597879A|1986-07-01|Micellar slug for oil recovery

---

SU1378788A3|1988-02-28|Micellar solution for extruding crude oil from bed

---

SU1419527A3|1988-08-23|Method of extracting petroleum from oil-bearing underground beds

---

CA1040409A|1978-10-17|Recovery of oil using microemulsions

---

CA1078160A|1980-05-27|Aqueous anionic surfactant systems

---

US4733728A|1988-03-29|Micellar slug for oil recovery

---

US4537253A|1985-08-27|Micellar slug for oil recovery

---

US4008769A|1977-02-22|Oil recovery by microemulsion injection

---

CA2732878A1|2010-02-25|Enhanced oil recovery using sulfonate mixtures

---

US4017405A|1977-04-12|Soluble oil composition

---

US3373808A|1968-03-19|Oil recovery process

---

Jamaloei2009|Insight into the chemistry of surfactant-based enhanced oil recovery processes

---

MX2013011104A|2013-10-17|Method and composition for enhanced hydrocarbon recovery.

---

US3920073A|1975-11-18|Miscible flooding process

---

GB2135713A|1984-09-05|Micellar slug for oil recovery

---

GB2138866A|1984-10-31|Micellar slug for oil recovery

---

US4460481A|1984-07-17|Surfactant waterflooding enhanced oil recovery process

---

US4534411A|1985-08-13|Micellar slug for oil recovery

---

US3324944A|1967-06-13|Miscible oil recovery process

---

US4556108A|1985-12-03|Micellar slug for oil recovery

---

US4765408A|1988-08-23|Micellar slug for oil recovery

---

US4192382A|1980-03-11|High conformance enhanced oil recovery process

---

US3994342A|1976-11-30|Microemulsion flooding process

---

GB2139270A|1984-11-07|Micellar slug for oil recovery

同族专利:

---

公开号 | 公开日

---

JPS5915185A|1984-01-26|

---

GB2123882B|1985-07-24|

---

CA1217928A|1987-02-17|

---

GB8318567D0|1983-08-10|

---

US4549607A|1985-10-29|

---

JPH0135157B2|1989-07-24|

---

GB2123882A|1984-02-08|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

RU2737429C2|2016-05-31|2020-11-30|Као Корпорейшн|Liquid detergent composition for textile products|

---

RU2748253C2|2016-12-26|2021-05-21|Као Корпорейшн|Method for treatment of textile product|US3477511A|1968-09-13|1969-11-11|Marathon Oil Co|Process for the recovery of petroleum using soluble oils|

---

CA1026666A|1974-12-24|1978-02-21|Joe B. Parmley|Secondary recovery process and surfactant compositions useful therein|

---

US4393937A|1981-03-25|1983-07-19|Shell Oil Company|Olefin sulfonate-improved steam foam drive|

---

GB2111559B|1981-10-09|1985-07-31|Lion Corp|Micellar slug for oil recovery|JPH0331871B2|1983-03-19|1991-05-08|Lion Corp|

---

US4732690A|1985-03-18|1988-03-22|Phillips Petroleum Company|Oil recovery composition|

---

US4612991A|1985-03-18|1986-09-23|Phillips Petroleum Co.|Oil recovery process|

---

US4662445A|1985-11-12|1987-05-05|Amoco Corporation|Method of increasing oil recovery by grading the ratio of monosulfonates and disulfonates|

---

US4811788A|1986-02-13|1989-03-14|The Standard Oil Company|Surfactant combinations and enhanced oil recovery method employing same|

---

US4957646A|1987-08-26|1990-09-18|Shell Oil Company|Steam foam surfactants enriched in alpha olefin disulfonates for enhanced oil recovery|

---

US5135052A|1991-03-28|1992-08-04|Exxon Production Research Company|Recovery of oil using microemulsions|

---

US5318710A|1993-03-12|1994-06-07|Chevron Research And Technology Company|Low viscosity Group II metal overbased sulfurized C16 to C22 alkylphenate compositions|

---

US5320763A|1993-03-12|1994-06-14|Chevron Research And Technology Company|Low viscosity group II metal overbased sulfurized C10 to C16 alkylphenate compositions|

---

US5320762A|1993-03-12|1994-06-14|Chevron Research And Technology Company|Low viscosity Group II metal overbased sulfurized C12 to C22 alkylphenate compositions|

---

EA021223B1|2008-02-07|2015-05-29|Шелл Интернэшнл Рисерч Маатсхаппий Б.В.|Method and composition for enhanced hydrocarbons recovery|

---

EP2250234B1|2008-02-07|2014-01-08|Shell Internationale Research Maatschappij B.V.|Method and composition for enhanced hydrocarbons recovery|

---

EP2240551A1|2008-02-07|2010-10-20|Shell Internationale Research Maatschappij B.V.|Method and composition for enhanced hydrocarbons recovery|

---

US8664167B2|2008-02-07|2014-03-04|Shell Oil Company|Method and composition for enhanced hydrocarbons recovery|

---

EA024070B1|2008-02-07|2016-08-31|Шелл Интернэшнл Рисерч Маатсхаппий Б.В.|Method and composition for enhanced hydrocarbons recovery|

---

US8940668B2|2009-04-16|2015-01-27|Shell Oil Company|Method and composition for enhanced hydrocarbons recovery from a very high salinity, high temperature formation|

---

CN102803433A|2009-05-05|2012-11-28|斯特潘公司|Sulfonated internal olefin surfactant for enhanced oil recovery|

---

WO2011005746A1|2009-07-09|2011-01-13|Shell Oil Company|Method and composition for enhanced hydrocarbon recovery from a formation containing a crude oil with specific solubility groups and chemical families|

---

CN103025996B|2010-05-22|2016-02-03|斯特潘公司|The method of recovering the oil from oil bearing bed|

---

WO2013030140A1|2011-08-31|2013-03-07|Shell Internationale Research Maatschappij B.V.|Composition and method for enhanced hydrocarbon recovery|

---

CN105092825B|2015-07-27|2016-11-16|中国石油天然气股份有限公司|A kind of screening technique of LOW PERMEABILITY RESERVOIR imbibition agent|

---

EP3388505B1|2015-12-10|2020-04-01|Kao Corporation|Surfactant composition|

---

RU2744265C2|2016-05-31|2021-03-04|Као Корпорейшн|Liquid detergent composition for textile products|

---

RU2747642C2|2016-05-31|2021-05-11|Као Корпорейшн|Detergent composition for textile products|

---

JP6894040B2|2017-04-06|2021-06-23|ニッサン ケミカル アメリカ コーポレイション|Hydrocarbon layer treated micelle solution|

---

JP2021006595A|2017-09-13|2021-01-21|日産化学株式会社|Crude oil recovery chemical|

---

EP3704205A1|2017-11-03|2020-09-09|Nissan Chemical America Corporation|Using brine resistant silicon dioxide nanoparticle dispersions to improve oil recovery|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

JP12449882A|JPH0135157B2|1982-07-19|1982-07-19|

---